Method for recovering rare earth, vanadium and nickel

ABSTRACT

A method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts, comprising steps of: acid leaching, by soaking waste vanadium-nickel catalysts into a sulfuric acid solution and obtaining a mixture containing alumina silica slag; sedimentation, by filtering out the alumina silica slag from the mixture to obtain a filtrate, and then adding a salt into the filtrate to precipitate rare earth followed by isolating a sediment of rare earth double salts and a liquid solution via filtration; and extraction, by providing and adding an alkali into the sediment of rare earth double salts followed by further soaking the rare earth double salts in an acid solution to precipitate rare earth, and adding an oxidizer into the liquid solution to adjust the pH value thereof and then extracting vanadium and nickel from the liquid solution via an ion-exchange resin.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for recovering metals from waste catalysts, particularly to a method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts.

2. Description of the Related Art

In oil-refining industry, catalysts have been widely used in oil-cracking processes, for example fluidized catalytic cracking (FCC), or residue oil cracking (ROC).

During the cracking processes, the FCC and ROC are easy to be ineffective due to the contamination and absorption of heavy metals from feedstock oil, and therefore, a great amount of waste FCC and ROC catalysts are generated and which will leads to damages to environment if a proper waste-treatment has not been gone through.

In conventional arts, the waste-treatments of the waste FCC and ROC catalysts are mainly relied on clacination or landfill. In frankly, it is pity, also risky to discard those waste FCC and ROC catalysts without any further treatment, since the waste FCC and ROC catalysts are rich in metals, such as vanadium, nickel or rare earth, and those metals may result in serious pollutions or ecological crisis for a long time.

Besides, rare earth is an important material in modern industries, and is generally used in nonferrous metallurgy industries, atomic energy industries, and petrochemical industries. In conventional arts, rare earths are recovered from waste catalysts via a roasting-acid leaching method, by roasting the rare earth at 600° C. to 700° C. under the performance of sodium carbonate, acid leaching rare earth with sulfuric acid, and finally precipitating and isolating rare earth with double salts.

However, the roasting-acid leaching method is poor in efficiency, with only 2% to 5% of rare earth recovered from the waste catalysts, and requires lots of heats and accessory materials, so that it is less effectively and less economically in industrial used.

Another conventional method to recover rare earth disclosed in CN101705380A and entitled as “A METHOD FOR RECOVERING RARE EARTH FROM RARE EARTH-CONTAINING ALUMINUM-SILICON MATERIALS” uses similar stratagem to recover rare earth and comprises processes of roasting, oxidizing, acid leaching and precipitating with double salts. Yet, the conventional method shares the same disadvantages as what it is described in above paragraph. Also, the conventional method has poor contribution to recovering vanadium and nickel from the waste catalysts either.

Hence, there is a need of improving the conventional technique and developing a cost-and-time saving method for recovering vanadium, nickel and rare earth from waste catalysts.

SUMMARY OF THE INVENTION

The primary objective of this invention is to provide a method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts, in which rare earth, vanadium and nickel in high quality can be efficiently recovered through a time-saving and cost-benefit process.

The secondary objective of this invention is to provide a method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts, by recovering useful metals from the waste catalysts produced by oil-refining industries so as to be eco-friendly.

Another objective of this invention is to provide a method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts, in which the recovering of metals can be achieved in an easy and user-friendly platform.

A method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts, comprising steps of: acid leaching, by soaking waste vanadium-nickel catalysts into a sulfuric acid solution and obtaining a mixture containing alumina silica slag; sedimentation, by filtering out the alumina silica slag from the mixture to obtain a filtrate, and then adding a salt into the filtrate to precipitate rare earth followed by isolating a sediment of rare earth double salts and a liquid solution via filtration; and extraction, by providing and adding an alkali into the sediment of rare earth double salts followed by further soaking the rare earth double salts in an acid solution to precipitate rare earth, and adding an oxidizer into the liquid solution to adjust the pH value thereof and then extracting vanadium and nickel from the liquid solution via an ion-exchange resin.

Further scope of the applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferable embodiments of the invention, are given by way of illustration only, since various will become apparent to those skilled in the art from this detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will become more fully understood from the detailed description given hereinbelow and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, and wherein:

FIG. 1 is a diagram illustrating a method for recovering rare earth, vanadium and nickel from waste catalysts in the present invention;

FIG. 2 is another diagram illustrating a method for recovering rare earth, vanadium and nickel from waste catalysts in the present invention.

All figures are drawn for ease of explaining the basic teachings of the present invention only; the extensions of the figures with respect to number, position, relationship, and dimensions of the parts to form the preferred embodiment will be explained or will be within the skill of the art after the following teachings of the present invention have been read and understood. Further, the exact dimensions and dimensional proportions conforming to specific force, weight, strength, and similar requirements will likewise be within the skill of the art after the following teachings of the present invention have been read and understood. Furthermore, when the term “first”, “second” and similar terms are used hereinafter, it should be understood that these terms are reference only to the structure shown in the drawings as it would appear to a person viewing the drawings and are utilized only to facilitate describing the invention.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with FIG. 1, there is a preferable embodiment of the method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts, which comprises a step of “acid leaching S1,” a step of “sedimentation S2,” and a step of “extraction S3.”

In the step of “acid leaching S1,” waste vanadium-nickel catalysts are prepared and soaking into a sulfuric acid solution to obtain a mixture in which contains alumina silica slag. Precisely, the waste vanadium-nickel catalysts are mainly collected from oil-refining industries and are rich in rare earth, vanadium and nickel. Through soaking the waste vanadium-nickel catalysts into the sulfuric acid solution, a great amount of the alumina silica slag will produce due to the inaction between insoluble parts of the waste vanadium-nickel catalysts, such as aluminum and silica, and the sulfuric acid solution. Meanwhile, the oxidization of sulfuric acid releases lots of heats which can not only maintain the reaction temperature at a proper range during the acid leaching without additional energy-supplement, but also avoid the interference of the alumina silica slag with the isolation of rare earth, vanadium and nickel. In the present invention, the concentration of the sulfuric acid solution is preferably adjusted at 1M to 5M, and the step of “acid leaching S1” is particularly preferably carried out at 90° C. to 95° C. for 1 to 4 hours, in order to produce maximum amount of alumina silica slag. The alumina silica slag produced the step of “acid leaching S1” in the present invention is easy to be isolated, recovered and manufactured into firebricks, so as to be significantly eco-friendly.

In the step of “sedimentation S2,” the alumina silica slag is filtered out from the mixture to obtain a filtrate, as following, a salt is prepared and added into the filtrate to precipitate rare earth, and finally a sediment of rare earth double salts and a liquid solution are isolated via a filtration, wherein the liquid solution comprises mass amount of metals, such as vanadium and nickel, leached from the waste vanadium-nickel catalysts. Specifically, the great amount of alumina silica slag produced in the step of “acid leaching S1” is filtered out at first to obtain a filtrate being rich in rare earth, vanadium and nickel. In the preferable embodiment, 5% to 20% of the salt is added into the filtrate, with the salt reacting and precipitating the rare earth, to produce the sediment of rare earth double salts. Therefore, the sediment of rare earth can be successfully isolated from liquid solution through the filtration due to its solid phase. In the present invention the salt can be selected from sodium sulfate, sodium chloride, ammonium sulfate or ammonium chloride, in order to produce double salts for precipitating rare earth in the step of “sedimentation S2.

In the step of “extraction S3,” an alkali is prepared and added into the sediment of rare earth double salts followed by further soaking the rare earth double salts into an acid solution to precipitate rare earth. On the other hand, an oxidizer is also prepared and added into the liquid solution to adjust the pH value thereof, and then, vanadium and nickel in the liquid solution are extracted via an ion-exchange resin. In general, various metals, particularly to rare earth, vanadium and nickel, can be extracted via any possible extracting processes in a random ranking according to the requirements of operators in the step of “extraction S3,” for the sake of obtaining metals in high quality and content. In the present invention the processes to extract vanadium, nickel and rare earth is obvious to one who has ordinary skill in the art, therefore, only a simple description is provided herein.

With reference to FIG. 2, the step of “extraction S3” comprising three substeps, including a substep of “precipitating rare earth S31,” by precipitating rare earth from the sediment of rare earth double salts; a substep of “extracting vanadium S32,” by extracting vanadium from the liquid solution; and a substep of “extracting nickel S33,” by extracting nickel from the liquid solution.

Precisely, in the substep of “precipitating rare earth S31,” the alkali is added into the rare earth double salts, with the alkyl replacing the double salts in the rare earth double salts and obtaining a caustic rare earth, followed by acid leaching the caustic rare earth with an acid. With such arrangement, the insoluble parts of the caustic rare earth are easily filtered out and a filtrate solution, comprising a significant amount of rare earth, is obtained. Therefore, it is sufficient to precipitate and obtain rare earth by adding a precipitin, oxalic acid or ammonium bicarbonate for example, into the filtrate solution. In the present invention, rare earth oxalate or rare earth carbonate are precipitated and obtained at the end. It is notice that the alkali of the present invention is selected but not limited to 3% to 20% sodium hydroxide, and the precipitin of the present invention is selected but not limits to oxalic acid or ammonium bicarbonate.

Next, in the substeps of “extracting vanadium S32” and “extracting nickel S33,” the oxidizer is prepared and added into the liquid solution, in order to adjust the pH value thereof at a proper range, and then vanadium and nickel in the liquid solution are sequentially isolated by using an ion-exchange resin. Specifically, in the substep of “extracting vanadium S32,” the pH value of the liquid solution is adjusted to 1 to 2, and the ion-exchange resin is selected from a type of D201, D290 or 947, for the sake of recovering vanadium in a good efficiency. Moreover, in the substep of “extracting nickel S33,” the pH value of the liquid solution is further adjusted to 5 to 6, with aluminum salts in the liquid solution being precipitating and filtered out at first, followed by isolating and recovering nickel through an ion-exchange resin in a type of 9333, XFS4195 and 122*3. In the present invention the oxidizer is selected but not limit to oxygen, air, manganese dioxide, potassium permanganate, ozone or hydrogen peroxide.

Finally, an additional step can be performed at the end of the present invention to neutralize a residue left from the step of “extraction S3,” by providing a small amount of calcium carbonate or calcium oxide to neutralize the residue and obtaining innocuous calcium sulfate which can be easily filtered out through another filtration. In this way the residue left in the present invention will become less polluted and able of being discarded in conforming to the environmental regulations.

For proving the efficiency of the present invention the leaching rate of rare earth, vanadium, nickel and alumina silica slag is monitored and recorded under various conditions, such as various concentrations of sulfuric acid and various times of acid leaching, in the following paragraphs. Referring to TABLE 1, 1000 grams of waste vanadium-nickel catalysts is prepared and soaking in 1M, 2M, 3M, 4M, or 5M of sulfuric acid at 95° C. for 2 hours to obtain the mixture, followed by filtering out alumina silica slag from the mixture to obtain filtrates, wherein the waste vanadium-nickel catalysts comprises 48% aluminum oxide, 15% silica, 0.5% vanadium, 0.4% nickel and 4% rare earth. In the present embodiment, the contents of the filtrates are analyzed and listed in TABLE 1.

TABLE 1 Contents of Filtrates under Various Concentration of Sulfuric Acid Leaching Concentrations of Sulfuric Acid Rate (%) 1 2 3 4 5 Aluminum oxide 11 17 23 23 29 Silica 0.2 0.2 0.2 0.2 0.2 Vanadium 57 79 98 98 99 Nickel 61 86 90 91 91 Rare earth 47 74 92 95 95

In TABLE 1, it is noted that the leaching rate of rare earth, vanadium and nickel all reaches 90% when the concentration of the sulfuric acid is more than 3M. It is suggested that heats and acidity both increase with the concentration of the sulfuric acid, and which is beneficial for not only the leaching of vanadium, nickel and rare earth but also maintaining the temperature at a preferable range during the leaching.

Referring to TABLE 2, 1000 grams of waste vanadium-nickel catalysts is prepared and soaking in 3M sulfuric acid at 95° C. for 1, 2, 3, or 4 hours to obtain the mixtures, followed by filtering out alumina silica slag from the mixtures to obtain filtrates, wherein the waste vanadium-nickel catalysts comprises 48% aluminum oxide, 15% silica, 0.5% vanadium, 0.4% nickel and 4% rare earth. In the present embodiment, the contents of the filtrates are analyzed and listed in TABLE 2.

TABLE 2 Contents of Filtrates under Various Leaching times Time of Acid Leaching Leaching Rate (%) 1 2 3 4 Aluminum oxide 15 22 23 23 Silica 0.1 0.1 0.1 0.1 Vanadium 70 97 98 98 Nickel 77 90 90 91 Rare Earth 81 91 92 92

In TABLE 2, it is noted that the leaching rate of rare earth, vanadium and nickel all reaches to 90% when the leaching time is longer than 2 hours. It is believed that 2 hours of acid leaching is enough to obtain a maximum amount of vanadium, nickel and rare earth in high quality since fewer amounts of rare earth, vanadium and nickel are leached out in a longer time.

In order to further verify the effects of the present invention, the same waste vanadium-nickel catalysts, being 1000 grams in weight and comprising 48% aluminum oxide, 15% silica, 0.5% vanadium, 0.4% nickel and 4% rare earth, are prepared again and processed according to the method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts in the present invention, and a sediment of rare earth double salts obtained from the step of “sedimentation S2” and labeled as “A;” and a filtrate solution obtained from the substep of “precipitating rare earth S31” and labeled as “B” are collected and analyzed respectively. Finally, the recovering rate of rare earth obtained from the filtrate solution “B” is also analyzed and labeled as “C.” In specifically, the waste vanadium-nickel catalysts are soaked into 3M sulfuric acid at 95□ for 2 hours, followed by filtering out alumina silica slag to obtain a filtrate. After that, 10% ammonium sulfate is added to the filtrate, and the sediment of rare earth double salts “A” and a liquid solution are obtained. In the present embodiment, the rare earth double salts “A” further reacts with 6% alkali solution and 10% hydrochloride acid to obtain the filtrate solution “B” after filtering out some insoluble parts therein. Finally, the rare earth in the filtrate solution “B” is precipitated and recovered by adding oxalic acid or ammonium bicarbonate, and the recovering rate of rare earth from the filtrate solution “B” is “C.” The contents of the sediment of rare earth double salts “A,” and the filtrate solution “B,” and the recovering rate “C” of rare earth from the filtrate solution “B” are summarized in the TABLE 3.

TABLE 3 Contents of “A,” and “B,” and the recycling rate “C” (%) A B C Aluminum oxide 3.3 7.3 0 Vanadium 0.15 0.01 0 Nickel 0.11 0.005 0 Rare Earth 99 98 98.7

In TABLE 3, it is shown that a significant amount of rare earth can be obtained through the present invention, with a recovering rate higher than 95%. Also, the contents of alumina silica slag decreases by the processes of the present invention, so that the extraction of rare earth can be successfully achieved in a high efficiency without any disturbance from the alumina silica slag. Meanwhile, vanadium and nickel are completely left in the liquid solution, and which is sufficient to be recovered sequentially in the substep of “extracting vanadium S32,” and “extracting nickel S33,” by adjusting the pH value of the liquid solution to a range of 1 to 2/5 to 6, and extracting the vanadium/nickel via an ion-exchange resin in a type of 945/9333. In the present embodiment, the recovering rates of vanadium and nickel can reach to 95%, and 98% to 99% respectively. In additional, the aluminum oxide in the liquid solution can also be recycled through a form of hydrate.

In summary, through the present invention, a method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts is provided, with sulfuric acid accompanied with double salts acid leaching and precipitating metals from the waste vanadium-nickel catalysts, in which rare earth, vanadium and nickel in high quality can be effectively recovered via a time-saving and user-friendly platform. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts is mainly characterized in acid leaching and precipitating metals from the waste vanadium-nickel catalysts by using sulfuric acid and double salts so that the interferences caused by alumina silica slag will be avoided, and also heats releases due to the oxidization of sulfuric will maintain the temperature at a proper range for acid leaching. Therefore, it is believed that the method of the present invention is significantly frugal of cost and material, but highly efficient in recovering rare earth, vanadium and nickel. Furthermore, the method of the present invention not only can recover waste vanadium-nickel catalysts, but also can reduce the chemical pollution resulted from the conventional arts, with the residue left behind being easy to neutralize with a small amount of calcium oxide or calcium carbonate.

Although the invention has been described in detail with reference to its presently preferred embodiment, it will be understood by one of ordinary skill in the art that various modifications can be made without departing from the spirit and the scope of the invention, as set forth in the appended claims. 

What is claimed is:
 1. A method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts, comprising steps of: acid leaching, by soaking waste vanadium-nickel catalysts into a sulfuric acid solution and obtaining a mixture containing alumina silica slag; sedimentation, by filtering out the alumina silica slag from the mixture to obtain a filtrate, and then adding a salt into the filtrate to precipitate rare earth followed by isolating a sediment of rare earth double salts and a liquid solution via filtration; and extraction, by providing and adding an alkali into the sediment of rare earth double salts followed by further soaking the rare earth double salts in an acid solution to precipitate rare earth, and adding an oxidizer into the liquid solution to adjust the pH value thereof and then extracting vanadium and nickel from the liquid solution via an ion-exchange resin.
 2. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 1, wherein the step of extraction further comprises substeps of: precipitating rare earth, by precipitating rare earth from the sediment of rare earth double salts obtained from the step of sedimentation; extracting vanadium, by extracting vanadium from the liquid solution also obtained from the step of sedimentation; and extracting nickel, by extracting nickel from the liquid solution also obtained from the step of sedimentation.
 3. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 1, wherein the concentration of the sulfuric acid solution is adjusted to 1M to 5M in the step of acidic leaching.
 4. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 1, wherein the temperature of the step of acidic leaching is adjusted to 90° C. to 95° C. to soak the waste vanadium-nickel catalysts into the sulfuric acid solution for 1 to 4 hours.
 5. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 1, wherein the concentration of the salt in the filtrate is 5% to 20% in the step of sedimentation.
 6. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 1, wherein the salt is sodium sulfate, sodium chloride, ammonium sulfate or ammonium chloride.
 7. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 1, wherein the oxidizer is oxygen, air, manganese dioxide, potassium permanganate, ozone or hydrogen peroxide.
 8. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 2, wherein, in the substep of precipitating rare earth, a sodium hydrate is added into the rare earth double salts, with the sodium hydrate replacing the double salts and obtaining a caustic rare earth, followed by acid leaching the caustic rare earth with hydrochloride acid, filtering out insoluble parts of the caustic rare earth to obtain a filtrate solution, and adding oxalic acid or ammonium bicarbonate into the filtrate solution to precipitate rare earth oxalate or rare earth carbonate.
 9. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 8, wherein the concentration of the sodium hydroxide is 3% to 20% and the concentration of the hydrochloride acid is 5% to 30%.
 10. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 2, wherein, in the substep of extracting vanadium, the pH value of the liquid solution is adjusted to pH 1 to 2 by adding the oxidizer, and then vanadium is extracted from the liquid solution via the ion-exchange resin.
 11. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 10, wherein the type of the ion-exchange resin is selected from D201, D290 or
 947. 12. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 2, wherein, in the substep of extracting nickel, the pH value of the liquid solution is adjusted to pH 5 to 6 by adding the oxidizer firstly, next, aluminum salts in the liquid solution is precipitated and filtered out from the liquid solution, and nickel in the liquid solution is extracted via the ion-exchange resin finally.
 13. The method for recovering rare earth, vanadium and nickel from waste vanadium-nickel catalysts as defined in claim 11, wherein the type of the ion-exchange resin is selected from 9333, XFS4195 or 122*3. 